EP0344406B1 - Tl-based copper oxide superconductor - Google Patents
Tl-based copper oxide superconductor Download PDFInfo
- Publication number
- EP0344406B1 EP0344406B1 EP89102644A EP89102644A EP0344406B1 EP 0344406 B1 EP0344406 B1 EP 0344406B1 EP 89102644 A EP89102644 A EP 89102644A EP 89102644 A EP89102644 A EP 89102644A EP 0344406 B1 EP0344406 B1 EP 0344406B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- superconductor
- bao
- superconductors
- thin film
- cuo2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002887 superconductor Substances 0.000 title claims description 56
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title 1
- 239000005751 Copper oxide Substances 0.000 title 1
- 229910000431 copper oxide Inorganic materials 0.000 title 1
- 238000000034 method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 16
- 229910052797 bismuth Inorganic materials 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- 229910052738 indium Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910052716 thallium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910003438 thallium oxide Inorganic materials 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910008649 Tl2O3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QTQRFJQXXUPYDI-UHFFFAOYSA-N oxo(oxothallanyloxy)thallane Chemical compound O=[Tl]O[Tl]=O QTQRFJQXXUPYDI-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/087—Oxides of copper or solid solutions thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
- C04B35/4512—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing thallium oxide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0408—Processes for depositing or forming copper oxide superconductor layers by sputtering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0436—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic superconductors
- H10N60/857—Ceramic superconductors comprising copper oxide
Definitions
- the present invention relates to superconductors having high critical superconducting temperatures, and particularly to a Tl, In, Ca, Sb or Bi system superconductor capable of being used even at or above the liquid nitrogen temperature.
- Tl2Ba2Ca1Cu2Oy (commonly called “2212") and, Tl2Ba2Ca2Cu3Oy (commonly called “2223”).
- Tl2Ca2Ba2Cu3Oy is reported to have a maximum value of Tc (critical superconducting temperature) as high as about 120K.
- Fig. 1 shows the relationships between the electric resistance and the temperature as regards conventional Tl system superconductors.
- the curve shows the relationship between the electric resistance of Tl2Ba2Ca2Cu3Oy and the temperature. It has a value of Tc of about 110K.
- Tl has the high toxicity, and the natural resources of it are poor.
- most of conventional Tl system superconductors have a high Tl content, which present grave problems including difficulties in taking a measure for elimination of toxicity in an aspect of production technique, reducing the production cost, and securing the Tl resources.
- An object of the present invention is to solve the above-mentioned problems to thereby provide a Tl, In, Ga, Sb or Bi system superconductor having a low Tl content and hence a low toxicity which is nevertheless high in superconducting transition temperature.
- Another object of the present invention is to increase layers of Cu-O by reducing Tl content thereby improving superconductive characteristics of Tl system superconductors.
- a further object of the present invention is to decrease the toxity of the multi layers CuO system superconductors to substitute part of Tl with In, Ga, Sb or Bi.
- a superconductor comprises a composition represented by the formula: (Tl a M 1-a )Ba2Ca x Cu x+1 O y , wherein 0 ⁇ x ⁇ 10, 0 ⁇ a ⁇ 1, and M is chosen in the group comprising In, Ga, Sb and Bi.
- a superconductor has a composition represented by the formula: (Tl a M 2-a )Ba2Ca x Cu x+1 O y wherein 2 ⁇ x ⁇ 10, 0 ⁇ a ⁇ 2, and M is chosen in the group comprising In, Ga, Sb and Bi.
- Superconductors comprising the above compositions are Tl system superconductors having a lower Tl content than conventional Tl system superconductors and hence lower in toxicity attributed to Tl. Nevertheless, the critical superconducting temperatures of the superconductors are substantially the same as those of the conventional Tl system superconductors.
- Superconductors in the form of modifications of the above-mentioned superconductors wherein part of Tl is substituted with In, Ga, Sb or Bi are lower in toxicity than the conventional Tl system superconductors and substantially the same in critical superconducting temperature as the conventional Tl system superconductors.
- TlBa2Ca x Cu x+1 O y can be prepared either by the sintering process or by the sputtering process.
- BaO2 and CuO powders may be used instead of the BaCuO4 powder and CaO2 may be used instead of CaO.
- the starting material powders are mixed together at such a ratio as to provide a composition: Tl4Ba2Ca x Cu x+1 O y in principle.
- the mixture of the starting material powders may be formed into a fiber instead of the above-mentioned pellet.
- a superconductor is produced by a sputtering method using a Tl-Ca-Ba-Cu-O system target and a substrate temperature of around 500°C. Since the sputtered superconductor is lacking in Tl atom, the superconductor is baked in oxygen gas together with thallium oxide at 850-900°C to adjust the composition.
- Fig. 2 shows the relationship between the electric resistance and the temperature of an example of the superconductor according to the present invention.
- Fig. 2 reveals that the critical superconducting temperature thereof ranges from 120K to 131K.
- Tl content of TlBa2Ca3Cu4O y decreases to about 1/4 of that of a conventional Tl system superconductor (Tl2Ba2Ca l Cu2O y ).
- Tl with In, Ga, Sb or Bi as far as any customary powder sintering process is used.
- superconductors except a Tl system superconductor were produced by a process of reacting a solution of nitrates.
- nitrates of each of In, Ca, Ba and Cu are dissolved in water together with at such a ratio as to provide a compostion: InBa2Ca3Cu4O y , subsequently, the resulting solution is reacted by spraying it on an alumina substrate heated at 600°C to form an In system suprconductor.
- Tl, Ga, Sb, or Bi system superconductors may be produced by the same process of producing the In superconductors.
- a superconductor thin film may be formed by the sputtering process or the molecular beam epitaxial growth process which are suitable for forming a substance with a lamellar structure.
- a superconductor thin film containing no Tl is formed, and the film is treated in a Tl oxide gas to form a thin film of a superconductor containing Tl, this superconductor is the same as described above where in part of Tl is stubstituted with In, Ga, Sb or Bi.
- a superconductor thin film of In, Ga, Sb or Bi system containing no Tl is formed, when the step fo the treatment in a Tl oxide is dispensed with.
- a thin film of a superconductor substance of the kind as described above wherein Tl is substituted with In is formed according to the following procedure.
- Ca x Cu x+1 , BaO, In2O3 and BaO are repeatedly deposited in this order on an SrTiO3 substrate heated at about 700°C by using three targets respectively made of Ca x Cu x+1 O y or Ca x Cu x+1 O y containing about 5 % of Sr added thereto, BaO, and In2O3 to form a superconductor thin film having a composition: InBa2Ca x Cu x+1 O y and a simple tetragonal and lamellar perovskite structure.
- deposition ot a thin film in layers at a low temperature close to room temperature may be followed by an annealing treatment in oxygen at about 900°C to crystallize the deposited thin film and to form the superconductor film.
- the thin film of InBa2Ca x Cu x+1 O y thus formed by sputtering deposition is placed in a Tl oxide gas and treated therein at around 900°C to be able to form a thin film wherein part of Tl in TlBa2Ca x Cu x+1 O y is substituted with In.
- molecular and atomic layers of InO 1.5 , BaO, CuO2, Ca, CuO2, Ca, CuO2 and BaO are deposited in this order on a substrate to form a thin film having a four-Cu-layer structure and a high value of Tc.
- the thin film described just above is placed in a Tl oxide gas and treated therein at around 900°C as in the case of the sputtering process to be able to form a thin film wherein part of Tl in TlCa x Ba2Cu x+1 O y is substituted with In.
- Tc of superconductor thin films except of Tl system superconductor formed according to either of the above-mentioned procedures are lower at present than that of the unsubstituted Tl system superconductor as shown in Fig. 2.
- the value of Tc can be raised by optimizing the composition and the conditions used for the formation of a thin film.
- Thin films wherein part of Tl is substituted with Ga, Sb or Bi instead of In can also be formed using either of substantially the same procedures as described above.
- TlBa2Ca x Cu x+1 O y can also be prepared in any one of substantially the same manners as described above.
- the present invention can provide the following advantages.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP134909/88 | 1988-06-01 | ||
JP63134909A JPH01305816A (ja) | 1988-06-01 | 1988-06-01 | 高温超伝導体 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0344406A2 EP0344406A2 (en) | 1989-12-06 |
EP0344406A3 EP0344406A3 (en) | 1990-07-18 |
EP0344406B1 true EP0344406B1 (en) | 1996-05-29 |
Family
ID=15139365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89102644A Expired - Lifetime EP0344406B1 (en) | 1988-06-01 | 1989-02-16 | Tl-based copper oxide superconductor |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0344406B1 (ja) |
JP (1) | JPH01305816A (ja) |
DE (1) | DE68926549T2 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2004576C (en) * | 1988-12-05 | 1995-10-24 | Yasuko Torii | Oxide superconducting material, process for preparing the same and applications thereof |
GB2232664A (en) * | 1989-06-17 | 1990-12-19 | Atomic Energy Authority Uk | Oxide materials |
JPH0365512A (ja) * | 1989-08-02 | 1991-03-20 | Sumitomo Electric Ind Ltd | 高温超電導材料およびその作製方法 |
JP2748161B2 (ja) * | 1989-09-04 | 1998-05-06 | 株式会社日立製作所 | In―Ba―Y及び/又はCa―Cu―O系超電導物質 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988010009A1 (en) * | 1987-06-09 | 1988-12-15 | E.I. Du Pont De Nemours And Company | Improved process for making superconductors |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3889024T2 (de) * | 1987-07-13 | 1994-10-13 | Sumitomo Electric Industries | Verfahren zum Herstellen einer supraleitenden Dünnschicht. |
US4870052A (en) * | 1988-03-08 | 1989-09-26 | International Business Machines Corporation | Tl-Ca-Ba-Cu-O compositions electrically superconducting above 120 degree K and processes for their preparation |
JP2634187B2 (ja) * | 1988-04-13 | 1997-07-23 | 株式会社フジクラ | タリウム系酸化物超電導体の製造方法 |
JP2509672B2 (ja) * | 1988-05-20 | 1996-06-26 | 住友電気工業株式会社 | 複合酸化物系超電導材料の製造方法 |
JP2656855B2 (ja) * | 1989-12-28 | 1997-09-24 | ローガン,キャスリン・ブイ | TiB▲下2▼及びAl▲下2▼O▲下3▼の造形された発泡耐火性生成物並びにその製造方法 |
-
1988
- 1988-06-01 JP JP63134909A patent/JPH01305816A/ja active Granted
-
1989
- 1989-02-16 DE DE68926549T patent/DE68926549T2/de not_active Expired - Fee Related
- 1989-02-16 EP EP89102644A patent/EP0344406B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988010009A1 (en) * | 1987-06-09 | 1988-12-15 | E.I. Du Pont De Nemours And Company | Improved process for making superconductors |
Non-Patent Citations (3)
Title |
---|
Physical Review Letters, vol. 58, no. 9, 2 March 1987, pages 908-910, M. K. WU et al. : "Superconductivity at 93 K in a new mixed-phase Y-Ba-Cu-O compound system at ambient pressure" * |
Physical Review Letters, vol. 60, no. 16, 18 April 1988, pages 1657-1660, New York, US; R. M. HAZEN et al. : "100 K superconducting phases in the TL-Ca-Ba-Cu-O system" * |
Proc. MRS Intern. Meeting on Advanced Materials, May 1988, Tokyo; communication of H. IHARA et al. : "Superconductivity of new high-Tc Tl1-Ba2-Ca3-Cu4-O11 (1234) superconductor" * |
Also Published As
Publication number | Publication date |
---|---|
EP0344406A2 (en) | 1989-12-06 |
EP0344406A3 (en) | 1990-07-18 |
JPH0574531B2 (ja) | 1993-10-18 |
DE68926549T2 (de) | 1996-10-31 |
JPH01305816A (ja) | 1989-12-11 |
DE68926549D1 (de) | 1996-07-04 |
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